Shampoos



SHAMPOGS Armin l-liestand, Binningen, Switzerland, assignor to Cilia Limited, Basel, Switzerland, a Swiss company No Drawing. Filed June 22, 1965, Ser. No. 466,061 Claims priority, application Switzerland, Oct. 25, 196i, 12,333/61 14 Claims. (Cl. 252-152) This is a continuation-in-part of application Ser. No. 232,608, filed Oct. 23, 1962, now abandoned.

The present invention provides shampoos that contain (a) A cationic compound containing at least one aliphatic hydrocarbon residue with more than 7, preferably 11 to 18, carbon atoms, as well as at least one tertiary or quaternary nitrogen atom present in salt-like form, and

(b) A water-soluble reaction product of an alcohol with 6 to 11 carbon atoms having a branched hydrocarbon radical and whose main chain contains at least 5 carbon atoms, with up to 15 molecular proportions of ethylene oxide.

It is known to use in shampoos simultaneously cationic compounds andv ethylene oxide adducts derived from linear higher fatty alcohols, for example n-dodecyl alcohol. Compared with such known shampoos the preparations of the invention are distinguished by a vastly superior lathering power and stability of the lather.

The outstanding lathering power of the new shampoos is all the more surprising as the above-mentioned cationic components (a) and the non-ionic components (b) by themselves either have a completely inadequate or no lathering power at all on hair.

It is another surprising advantage of the preparations of the invention that their washing power is such that it ensures on one hand a completely adequate washing effect on dirty hair, while on the other hand this is not accompanied by an undesirable defatting, drying, irritation or the like of the hair or scalp respectively such as is connected with an excess washing effect.

The socalled poissage-efiect which often occurs on application of shampoos containing cationic ingredients and which finds its expression in hair sticking together, more especially when it is subsequently rinsed, practically does not crop up with the present shampoos. It is another of their advantages that they have no unpleasant odour of their own or one that would render perfuming difiicult.

Hair treated with one of the new shampoos has a soft, flufiy feel and a pleasing silky sheen, it has no electrostatic charge and is easy to brush and comb.

The store-mentioned valuable properties of the hair are obtained more especially with those preparations of the invention which contain a hair shampoo preparation which contains (1) As cation active component a member selected from the group consisting of (a) a tertiary amine salt of the compound of the formula R4 R,le lN R, N

3,322,676 Patented May 30, 11967 in which Where A and A each represents a member selected from the group consisting of a hydrogen atom, the

methyl radical and the hydroxyethyl radical with a cosmetically acceptable acid,

(b) A tertiary amine salt of a compound of the formula RrNR -N-R 0H, CH3

in which R represents an aliphatic hydrocarbon radical with 11 to 18 carbon atoms, and

R represents a member selected from the group consistting of an alkylene radical containing 2 to 6 carbon atoms and the radical -CH CHOH-CH with a cosmetically acceptable acid,

(0) A quaternary ammonium salt of a compound of the formulae set forth above under (a) and (b) with a member selected from the group consisting of methyl iodide, dimethyl sulfate, benzyl chloride, a polyglycol chloride containing at most 6 carbon atoms and ethylene chlorohydrine,

(d) A compound of the formula N-OH2 RW- (3H2 N if in which R represents a hydrocarbon radical With 11 to 18 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom, a radical of the formula -CH -CH -NH and a radical of the formula CHZCH2-OH (2) As nonionic component a water-soluble reaction product of an alcohol which contains 6 to 11 carbon atoms, whose hydrocarbon radical is branched and whose main-chain contains at least carbon atoms, with at most 15 mols of ethylene oxide,

(3) Water, and

(4) A cosmetically acceptable acid in an amount which is sufficient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to 1:100.

With regard to their non-ionic ingredient (2) those preparations of the invention deserve to be given preference which contain a compound obtained by reacting 5 to molecular proportions of ethylene oxide with 1 molecular proportion of the alcohol referred to above under (2).

Particularly useful are those new mixtures whose nonionic ingredient has been prepared by adding 5 to 10 molecular proportions of ethylene oxide on to a secondary or preferably primary aliphatic alcohol of the kind described above.

Surprisingly, it has further been found that those shampoos of the invention possess particularly good properties and are distinguished, for example, by the absence of an unpleasant odour of their own even when examined critically, which contain as the non-ionic ingredient an ethylene oxide adduct which, before being incorporated in the shampoo, has been subjected to a special purifying treatment, for example by expulsion of undesired substances by distillation. Such a purification operation may consist, for example, in the distillative expulsion from a commercial ethylene oxide adduct under a very good water-jet vacuum at about 160 to 180 C. or in a fallingfilm distillation. It has further been found that particularly valuable, purified products are obtained in this manner when the commercial ethylene oxide adduct liquefied by heating is mixed in the undiluted form with a sufficiency of an inorganic or organic acid to establish a weakly acidic reaction of the resulting solution of 10% strength. This may be achieved with concentrated acids, such as phosphoric acid of 85% strength, lactic acid of 90% strength, tartaric acid or citric acid. It is of special advantage to heat the batch to a distillation temperature corresponding to the boiling point of the monohydroxyethyl compound or of the monoglycol or diglycol ether of the alcohol selected as starting material.

The amine compound on which the cationic ingredient (a) is based can be prepared by methods known in the art from the corresponding amine bases or their reaction products with fatty acids or derivatives thereof, hydroxyalkylation agents, for example ethylene oxide, alkylating and acylating agents, for example chloracetic acid or with derivatives thereof, and then converted in known manner by reaction with acids into the amine salts or with quaternating agents into the quaternary ammonium salts. Suitable starting materials for the manufacture of the cationic ingredient to be used according to the invention are tertiary amines of the formula wherein R represents an alkyl with l2-l6 carbon atoms, for example, N-dimethyl-dodecylamine, N-dimethyl-hexadecylamine and their hydroxyalkylation products, also diamines, for example N-dodecyl-ethylenediamine, tetramethylenediamine and hexamethylenediamine, N-octadecyl-ethylenediamine, N-dodecyl-propylenediamine, N- hexadecyl-propylenediamine and N-octadecyl-propylenediamine; also reaction products of such N-alkylene-polyamines with an alkylene oxide, such as ethylene oxide or propylene oxide, for example N-dodecyl-N:N'-dihydroxyethyl-ethylenediamine, N dodecyl-N:N'-dihydroxyethylpropylenediamine and N-octadecyl-N:N-dihydroxyethylpropylenediamine. Furthermore, there may be used as starting material for the cationic ingredient (a) contamed in the new preparations the following: mono-acylation products from 1 molecular proportion of a higher fatty acid (for example lauric, myristic, palmitic, stearic or oleic acid) and 1 molecular proportion of an alkylenepolyamine such as ethylenediamine or propylcnediamine and diethylenetriamine; likewise suitable are reaction products of these monoacyl derivatives with a halohydrin or alkylene oxide, such as N-lauroyl-N-hydroxyethylethylenediamine, N palmitoyl-N'-hydroxyethyl-ethylenediamine, N-stearoyl-N-hydroxyethyl-ethylenediamine, N- lauroyl-N'-hydroxyethyl-propylenediamine and N-lauroylhydroxyethyl-diethylenetriamine.

Those compounds of the general Formula 1, which are used in the form of their salts as cationic ingredient (a) of the new preparations and contain a radical of the formula (in which formula A and A have the above meanings) are accessible by reacting the amine concerned with chloracetic acid or with a compound of the general formula (in which A and A have the above meanings), more especially with chloracetamide or NzN-[di-(fi-hydroxyethyl) l-chloracetamide.

The conversion of the selected tertiary amines into salts used as cationic ingredient of the new preparations is achieved by the usual formation of salts with cosmetically acceptable acids which may be inorganic, such as hydrochloric acid, and phosphoric acid, or organic acids as acetic acid, adipic acid, tartaric acid, malic acid, nitriletriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycolic acid and mixtures of the above-mentioned acidsv Quite generally speaking, any acid may be used that furnishes with the harmless amine salts that are neither toxic nor irritate the scalp, more especially the salts mentioned specifically below, such as are used in the present invention to establish the desired pH range.

To convert the tertiary amine compounds into quaternary ammonium compoundswhich may likewise and with special advantages be used as cationic ingredient of the new preparationsthey are reacted in known manner with a quaternating agent, for example methyl iodide, dimethyl sulfate, benzyl chloride or with ethylen hlorohydrin or with a polyglycol chloride.

It has further been found that the above-mentioned valuable properties of the new shampoos are particularly evident in those preparations in which the ratio of the cationic ingredient (a) to the non-ionic ingredient (b) ranges from 1:1 to 1:30, preferably from 1:2 to 1:10. More especially at a ratio of (a) (b) of 1:3 it was found that t the new preparations had surprisingly advantageous properties insofar as their lathering power and the stability of the lather, good washing power, gentleness towards the skin and absence of the poissage-effect are concerned.

When the above-mentioned ratios are used, the new preparations have a particularly long shelf-life.

The preparations of the invention should have a moderately acidic to neutral reaction, for example ranging from pH 3.0 to 7.0. The desired pH value may be adjusted with any inorganic or organic acidic compound acceptable for use in cosmetics, for example with acetic acid or phosphoric acid, or with acid phosphates, or adipic, tartaric, malic, nitrilotriacetic, ethylenediamine-tetra:

acetic, citric, lactic or glycolic acid.

Likewise suitable for this purpose are mixtures of inorganic and organic acids, for example mixtures of phosphoric acid and citric acid.

The new shampoos containing the new combinations are obtained by simply mixing and dissolving the ingredients, if desired with further addition of compounds conventionally contained in shampoos, such as perfume, dyestuffs, bleaching agents or thickening agents.

There may be further added fatty acid alkanol-amides, for example coconut oil fatty acid hydroxyethy -amide. The new preparations may be prepared in solid, pasty or liquid form. They are applied in the known hairdressing manner.

Very favourable results were obtained with hair shampoos of the composition set forth above in this application, wherein the weight ratio of cation-active component (l) to nonionic component (2) ranges from 1:1 to 1:100.

Parts in the following examples are parts by weight.

Example 1 (a) The non-ionic polyglycol ethers listed in the following Tables I to V were examined for their lathering power. The results are shown in the tables under Lather volume I.

(b) The cationic compounds listed in the following 6 Tables I to V were examined for their l'at'hering power. The results are shown in the tables under Lather volume II.

(c) Combinations of the cationic and non-ionic compounds shown in Tables I to V were examined for their lathering power. The results are shown in the tables under Lather volume C.

The amounts of the ingredients making up the combinations are shown in the tables under C; I refers to the percentage of the non-ionic share of the total weight of the shampoo solution, and II refers to the cationic share of the total weight of the solution. The remainder of the total weight is accounted for by water and the amount of acid necessary to establish the pH value.

The shampoo solutions listed in the following Tables I, II and V were prepared by dissolving the non-ionic compound and the cationic compound in water with addition of a sufiiciency of citric acid to establish a pH value of 4 to 4.5 of the individual solutions.

The term lather volume in the following Tables I to V refers to the amount of lather in cc. produced by twice washing 10 g. of homogeneously dirtied raw wool, moistened with g. water at C. with 2.7 cc. of the individual shampoo solution in each case. The indices 1 and 2 underneath lather volume in Tables I to V refer to the first and second wash each performed in the method employed for determining the lather volume.

TABLE I Lather volume in cc.

Non-ionic compounds I 2 ethylhexanol +5 mols ethylene oxide. 0

2-etl1ylhexunol +5 mols ethylene oxide O 0 3. 2-ethylhexanol +5 mols ethylene oxide 0 0 4. Isooctanol +5 mols ethylene oxide. 0 0

3:5:5-trlmethy1hexanol +5 mol ethylene oxide..... 0 0

6- 3:5:5-trlmethylhexanol +10 mol ethylene oxide... 0 0

Lather volume Lather volume 0 Cationic compounds containing a in cc.

quaternary nitrogen atom II I+II The cationic compound used in the mixtures shown in obtained by heating the compound Tabl eIwas C H N(CH for 24 hours at 100 C. with excess TABLE [I Lather Lather Lather Volume Cationic compounds containing a volume C volume Non-ionic compounds I quaternary nitrogen atom II I+H C H1O H OH 1- Z-ethylhexanol mol ethylene 0 C 2Hz5N-CH2CH2OH 011 0 O 0 0 0 12+4 100 210 oxide H 0 H H C HaC HzOH 2- do O Ci2H25N-CH2 Q Cl 0 0 12+4 cniomon C H; 3 .410 0 Ci2H251 ICzHiOH C1 5 10 12+4 320 0 H; 4 do 0 C11H23 C NHCz1'I6ll -CH3 CHaSO4' 5 l0 12+4 330 0 H CH 5- ..d0 0 C |iHz3( ]I ICaHuI TCH-]C 1' 0 0 12+4 105 275 NC H1 6 d0 0 C11Hz3( 1 (EH: (6 0 0 12+4 40 150 N CH2C NH'CZH4OH CzH4O H Cl CHCHzN-OH4OH C H; 7- "d0 0 C mHa3-CH3 B1" 0 0 l2+4 80 0 H; 8 do 0 oifiHail hczflioloiHlohH Cl 0 0 12+4 00 130 CH3 9. 2-ethylhexanol +5 mol ethylene 0 C1B 33I IC2H40[C2 40]3H Cl 0 0 12+4 70 150 oxide with addition of 2% by weight of polyvinyl pyri'oli- CH; Fl0f 0%%3%5%t%.' Weigh C H 10- Z-effiglhexanol +5 mol ethylene 0 CiaHaaI IIOHiCH;OH Cl- 0 0 l 12+4 125 240 1 The pH value of the solution is adjusted to 6.9.

TABLE IIIb Lather Lather Lather volume volume volume Cationic com pounds containing at least one C Non-ionic compounds I tertiary nitrogen atom II C I+II 1 2 1 2 1 2 (H) 2-ethylhexanol +5 mol ethylene oxide.-- 0 CIIH2SC+ NI'IC2H(\ 6 12+4 260 500 N H HO-C ;H +NO 1H.

H CN(O2H4O )1 i 2 do 0 0 O1IHZ3C+NH-C2H4 5 10 12+4 240 50 N 1 L H HO-CzH4*--NC2 4 0 CH2 (C H3) 2 Similar results are obtained by adjusting the combinations of Tables I to IIIb to a pH value from 4 to 4.5, instead of with citric acid, with one of the following acids: adipic, tartaric, phosphoric, lactic, acetic, ethyl- (I) N q compound (11) Cationic compound enediarnine-tetraacetic, nitrilotriacetic or glycollic acid.

Similar, very advantageous results with regard to CH3 I lathenng and.washmg. W? F Obtamed Wlth 2-propylheptonol +5 mols of ethylene CwHaaN-CzHAOH Claqueous solutions ad usted with citric acid to a pH value oxide 1 from 4 to 4.5, containing the following combinations of CH3 a non-ionic compound with a cationic compound: V 1

1-ethyl-, 3-ethyl l-heptanol +8 mols C1flH33N-C2H4OH Cl- (I) Non-ionic compound (II) Cationic compound of ethylene OXldB- AH 3 3H Q-ethylhexanol +5 mols of ethylene Lanrylamine +20 mole of oxide. propylene oxide. Q-ethglhexanol +10 mole of ethylene C1 H 3ITIC2H4OH 01-- $11 The weight ratios between the component I and the Isodecanol firnols of eth lenc ox1dc C H N-C H OH 01- y 2 4 component II are the same as those set forth above in Tables I to III. TABLE IV.EX.AMPLES OF COMBINATIONS OF (a) AND (17) USING DIFFERENT ACIDS Lather volume Share in Share in Share in percent Non-ionic compound I percent Cationic compound percent Acid component C of weight of weight of weight of the I of the II of the III 1+II+III solution solution solution (llH 1 12 3:5:5-t1imethylhexanol 4 CmHas-N-CHzOHzOIUCl 1 Adipic acid 380 +5 mols ethylene oxide.

. CH3 (EH 2 12 ---..d0 4 CmH3a-1IICH2CH2OH+CV 1 Tartaric acid (100%) 100 420 CH3 I i 3 i2 u do 4 C1aHaaIII-CH2CH2OH+CY 0.1 Phosphoric acid (85%)-.-. 160 320 CH: i 4 12 -..do 4 C1sHaaNCH2CHzOH+Cl 1 Ethylenediaminotetra- 380 I acetic acid (100%). CH (EH3 5 -e 12 .do 4 C1aI'I3aNCH2CH2OH C1 2 Nitrilotriacetic acid 180 360 1 With 2% coconut oil fatty acid ethuuolamide.

3,322,676 15 16 The following Table V shows that combinations in a side-chain of fewer than 5 carbon atoms or derived which the non-ionic ingredient is a compound derived from an alkylphenol do not possess the advantageous from a linear alcohol or from a branched alcohol having properties of the preparations of the invention.

TABLE V Lather Lather Luther volume volume volume Cationic compounds containing C Non-ionic compounds I a quaternary nitrogen atom II I H C 2-ethylbutanol mol ethylene oxide O 0 CmH;5lliCzH4OH]+ Cl C Hz n-Octanol +5 mol ethylene oxide 0 0 C1tH351 lC2H OH]+ Cl 5 0 Ha Tert. nonylphenol +8 mol ethylene oxide 0 I 0 C sH I ICzH4OH]+ Cl 5 5 12+; 0 0

C Ha Lauryl alcohol +7 mol ethylene oxide 0 O C1GII3B}\IIC2HLOI{]+ C1 5 5 12+4 o 0 CH3 Lauryl alcohol +12 mol ethylene oxide 0 0 CiuH' 5I I-CzH4OI-I]+ Cl 5 5 12+; 0 0

C H; Steeryl alcohol +8 mol ethylene oxide 0 0 C1tH 5l I-C 2H40H1+ Cl 5 5 l2+4 0 0 C H; D0 0 0 C1bH35I IC2H4OH] Cl 5 5 l2+4 0 0 CH3 Do i 0' 0 C1eHa5I l-Cz 4 5 5 0 0 7 0 H3 2-ethylbuten01 +5 mol ethylene oxide +160 mol ethylene oxide 0 0 C1dH35 l C2H4OH] C1 5 5 12+; 0

1 Plus mol ethylene oxide. 1 Plus mol ethylene oxide.

Example 2 case with the thickening agents shown in Tables VI and A shampoo was made of the composition of the product VII: l in Table I. This shampoo was further admixed in each TABLE VI Non-ionic compound Cationic compound Substance acting as thickening agent Viscosity,

25 in I II III I+II+III centipoises E 0 2-ethylhexanol mols buH33N(1HzCH20H]+ Cl 12 4 0 3 ethylene oxide. 1

I C 3 1" 1 wdo O; H35NCHCHOH]+ C1 Stearyl alcohol +80 mols ethylene oxide 12 4 0H 1 2 "do CmHaalTI-CHzCHzOHI' Cl Stearyl alcohol +200 mols ethylene oxide 12 4 78 CH: 5 3 do C10H33N-CH2CH2OH1+ Cl Hydroabletyl alcohol +200 mols ethylene 12 4 10 22 I oxide. 12 4 20 61 CH 5 ('hgH gN-CHzCH OHF C1 Reaction product of (a) oleyl alcohol +80 111015 12 4 5 22 of ethylene oxide with (b) hexamethylene 12 4 7.5 68 H diisocyanatew 12 4 10 200 12 4 20 1,600 5 do ClflHaalII-OHQCHZOHIH Cl Polyethylene glycol (mean molec.wt.20,000). 4 1(5) CH3 E 6 d0 CmHaaIII-CHzOHzOHP 01 A hydroxylated cellulose 12 4 1 CH; 5 7 do C1flH33N CH2c/H2OH] Cl Finely dispersed silicic acid (AerosiY, reg. 12 4 5 trade name).- 12 4 10 CH3 1 Paste (brushable).

TABLE VII Non'ionic compound Cationic compound Substance acting as thickening agent 0 Viscosity,

25 in I II III I+II+III centipoises 5 1 2-ethylhexano1 +5 mol C1aH3 NOHzCHOH]+ Cl Stearylarnine mol ethylene oxide 12 4 10 15 ethylene oxide.

CH3 5 2 do C10H33NCH2CH2OH]+ Cl Oleylamine +80 mol ethylene oxide 12 4 10 17 a E 3 do CmHaaIIl-CHzCHzOHH Cl Stearylamine mol ethylene oxide 4 10 18 4 20 50 CH3 4 do C1 H 3NCH CH 0H]+ 01 A reaction product of 1 mol coconut oil fatty 12 4 5 64 acid and 2 mols diethanolamine, with elimi- CH nation of 1 mol water.

1 9 Mixtures having very valuable properties are also obtained by adding 2% 4% and 8% of polyvinylpyrrolidone (molecular weight 400,000 to 700,000).

20 Example 4 (a) The non-ionic polyglycol ether, listed in the following Tables VIII to X, was freed in a falling-film Example 3 evaporator from the unreacted alcohol and the monoglycol and diglycol ethers and then examined for its lathering The shampoos listed in Tables I to IV of Example 1 power. The results are shown in the Tables VIII t X were examined as to whether they displayed the s-o-called u d th h ading Lather volume I, pissage-etfect. As is known, this effect consists in the (b) The cationic compounds listed in the following following: When hair washed with a shampoo containing 10 Tables VIII to X were examined for their lathering power. a cationic compound and then rinsed with water, salve- The results are shown in the Tables VIII to X under the like, water-insoluble deposits form on the hair and, more heading L ther volume 11, especially in the case of womens long hair, cause it to (c) The combinations of cationic compound and nonstick. The occurrence of this sticking eifect (pissage) ionic compound listed in the Tables VIII to X were exseems to be due to the anionic constituents of the dirt amined for their lathering power. The result is listed in found on human hair. Tables VIII to X under Lather volume C. The amounts In the in vitro tests 18 g. of hair dirtied with 10% of of the ingredients are shown in the Table under C," in oleic acid was washed in each case with 5 g. of the which I is the percentage share of the non-ionic comshampoos listed in the Tables I to IV and then rinsed. pound of the total weight of the shampoo solution, and It was found that after washing at 35 C. and rinsing, 20 II is that of the cationic compound. The remainder of the combinations listed in Tables I to IV produced subthe total weight is accounted for by water and the amount stantially no sticking of the hair. of acid needed to adjust the pH value.

TABLE VIII Lather Lather Lather volume volume volume Cationic compounds containing a quaternary O Non-ionic compounds I nitrogen atom II C I+II (3115 1 2-ethy hexanol +5mol ethylene oxide 0 0 C12Hz -NCHgCONH;]Cl 0 0 l2+4 115 240 2 do 0 0 CnHI IOH CONHCJLOHPOP 0 0 12+4 195 380 CH;

E a do 0 0 C12Hasl lT-CHz(/ONC H Cl 0 0 12+4 160 CH3 CHaCHzOH 5 4 do 0 0 c,,]-1 -I ICHiC0NH,]+o1' 0 o 12+4 240 CH; w 5 do 0 0 CitHsaIIF-CHzCONHCzH4OH]+Cl' 0 0 12+; 105 190 TABLE IX Lather Lather Lather volume volume volume Cationic compounds containing a quaternary C Non-ionic compounds I nitrogen atom II C I+II ii 1 I ii 1 2-etlylhexanol +5 mol ethylene 0 0 O11H GN(CH2)aN-OHONH; 0 0 12-1-4 150 280 2 do 0 0 CnHzaOONH(CHz)a1T-CH:CONHC2H OH]+ Cl 0 0 12+4 240 CH; ([JH: 3 ...d0 O O 617E350ONH(CHz)3N-CH3CH:OH]+ Cl 0 0 12-1-4 105 210 The shampoos set forth above in Tables VIII and IX were adjusted with citric acid to a pH-value of 4.0 to 4.5, with the exception of those signified by which were adjusted with citric acid to pH-value of 6.9.

Good results were also obtained with shampoos of the compositions set forth above in Tables I to IV and VI to 1X when the nonionic (1) and the cationic (2) compounds were used in weight proportions different from those set forth specifically in the said tables but lying Within the range of 2:1 to 10: 1.

Example 5 (a) The following mixture was prepared:

4 parts of a mixture of 1 mol of coconut fatty .acid diethanolamide and 1 mol of diethanolamine, 25 parts of a condensatoin product containing 1 mol of Z-ethylhexanol and about 8 mols of ethylene oxide, 0.25 part of cetyldimethyl-(2-hydroxyethyl)-ammonium chloride,

2.5 parts of about 88% lactic acid,

3 parts of polyethylene glycol having a molecular weight of about 20,000.

The mixture was made up to 100 parts with water and a shampoo obtained to which perfumes can be added, if desired.

What is claimed is:

1. A hair shampoo preparation which consists essentially of 1) the cationic compound of the formula (2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, Whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide,

(3) water, and

(4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraa-cetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufiicient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0,

and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to 1:100

2. A hair shampoo preparation which consists essentially of (1) a cationic compound of the formula CH3 CH3 [C12 2P T( 2)n-I TC12 2s 2X CH3 CH3 wherein n represents a number from 2 to 6 and X- represents a halogen anion selected from the group consisting of chlorine and bromine,

(2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, Whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide,

(3) water, and

(4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof in an amount which is sufiicient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0,

and in which shampoo preparation the weight ratio of component (1) to component (2.) ranges from 1:1 to 1:100.

3. A hair preparation which consists essentially of (1) a tertiary amine salt of a cationic compound of the formula wherein R represents a-lkyl with 12 to 16 carbon atoms with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid; malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, (2) a nonionic water-souble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is suflicient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:2 to 1:100.

4. A hair shampoo preparation which consists essentially of (1) a tertiary amine salt of the cationic compound of the formula with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, (2) a nonionic Water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufficient to effect in the shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to 1:100.

5. A hair shampoo preparation which consists essentially of (1) a tertiary amine salt of the cationic compound of the formula with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof,

(2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, whose main-chain consists of at least carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufficient to effect in the aqueous shampoo preparation a pH-vaue of 3.0 to 7.0, and in which shampoopreparation the weight ratio of component (1) to component (2) ranges from 1:1 to 12100.

6, A hair shampoo preparation which consists essentially of (1) a tertiary amine salt of the cationic compound of the formula with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid,

adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof,

(2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 car bon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide,

(3) water, and r (4) :a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufficient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0,

and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to

7. A hair shampoo preparation which consists essentially of (1) a tertiary amine salt of the cationic compound of the formula with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, (2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 car- 'bon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufiicient to eifect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to 1:100.

8. A hair shampoo preparation which consists essentially of (1) a tertiary amine salt of the cationic compound of the formula with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, (2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufficient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of component (1) to component (2) range from 1:1 to 1:100.

9. A hair shampoo preparation which consists essentially of (1) a tertiary amine salt of the cationic compound of the formula wherein n represents a whole number of at most 2, with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, (2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, in an amount which is sufficient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of com aonent (l) to component (2) ranges from 1:1 to 1:10

10. A hair shampoo preparation which consists essentially of (1) a cationic compound selected from the group consisting of (a) a tertiary amine salt of a compound of the formula R4 R, 6 N-Jh N in which n represents a number of at most 2, m represents a number of at most 3, R represents alkyl with 11 to 18 carbon atoms, R represents alkylene with 2 to 6 carbon atoms, R R and R each represent a member selected from the group consisting of hydrogen, alkyl with at most 2 carbon atoms, hydroxyalkyl with at most 3 carbon atoms,

CH2C ON where A and A each represents a member selected from the group consisting of hydrogen, methyl and hydroxyethyl, with a cosmetically acceptable acid selected from the group consisting of acetic acid, phosphoric acid, adipic acid, tartaric acid, malic acid, nitrilotriacetic acid, ethylene-diamine-tetraacetic acid, citric acid, lactic acid, glycollic acid and mixtures thereof, and (b) a quaternary ammonium salt of a compound of the formula set forth above under (a) with a member selected from the group consisting of methyl iodide, dimethyl sulfate, benzyl chloride, a polyglycol chloride containing at most 6 carbon atoms and ethylenechlorohydrine, (2) a nonionic watersoluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms, whose main-chain consists of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide, (3) water, and (4) a cosmetically acceptable acid, as defined above in this claim under (a) in an amount which is sufficient to effect in the aqueous shampoo preparation a pH-value of 3.0 to 7.0, and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to 1:100.

11. A hair shampoo preparation which consists essentially of (1) a cationic quaternary ammonium salt of a compound of the formula atoms and R and R represents alkyl with at most 2 carbon atoms with ethylenechlorohydrine,

(2) a nonionic water-soluble reaction product of a saturated branched-chain alcohol with 6 to 11 carbon atoms whose main-chain consist of at least 5 carbon atoms, with 5 to 15 mols of ethylene oxide,

(3) water, and

(4) a cosmetically acceptable acid as defined above in claim 10 under (a) in an amount which is suflicient to effect in the aqueous shampoo preparation a pH value of 3.0 to 7.0,

and in which shampoo preparation the weight ratio of component (1) to component (2) ranges from 1:1 to 1:100.

12. A preparation as claimed in claim 10 which contains as further component approximately 5% by weight of a mixture of coconut fatty acid diethanolamide and diethanolamine.

13. A preparation as claimed in claim 10 which contains as a further component an eifective amount of a mixture of coconut fatty acid diethanolamide and diethanolamine as a thickening agent.

14. A preparation as claimed in claim 10 which contains as a further component approximately 120% by weight of a thickening agent.

References Cited UNITED STATES PATENTS 2,669,546 2/ 1954 Zussman et al. 252-153 2,877,178 3/1959 Bergman et al. 2,913,417 11/1959 Weeks 252-152 2,934,568 4/1960 Barker 252-152 X 2,961,451 11/ 1960 Keough 167-87 X 2,965,678 12/ 1960 Sundberg et al. 167-87 X 2,999,068 9/ 1-961 Pilcher et al. 252-152 X 3,003,969 10/1961 Albrecht 252-152 X 3,072,690 1/ 1963 Lee et a1. 3,086,943 4/ 1963 Lang 252-152 3,098,794 7/ 1963 Dohr et al. 167-87 3,156,656 I l/1964 Libby 252-152 3,198,828 8/1965 Matter 167-87 X 3,202,714 8/1965 Zimmerer et al. 252-152 X FOREIGN PATENTS 1,062,392 7/ 1959 Germany. 1,083,504 6/ 1960 Germany.

815,784 7/1959 Great Britain.

818,361 8/1959 Great Britain.

LEON D. ROSDOL, Primary Examiner. ALBERT T. MEYERS, Examiner. S. E. DARDEN, Assistant Examiner. 

1. A HAIR SHAMPOO PREPARATION WHICH CONSISTS ESSENTIALLY OF (1) THE CATIONIC COMPOUND OF THE FORMULA
 10. A HAIR SHAMPOO PREPARATION WHICH CONSISTS ESSENTIALLY OF (1) A CATIONIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) A TERTIARY AMINE SALT OF A COMPOUND OF THE FORMULA 